KR20040110873A - The efficient synthetic method of N,N-diglycidylalkylamine - Google Patents

Abstract

PURPOSE: A method for preparing N,N-diglycidylalkylamine by using alkylamine and epihalohydrin is provided. The preparation method thereof is carried out at room temperature without using phase transition catalyst. Therefore, the yield and purity of N,N-diglycidylalkylamine are improved. CONSTITUTION: The method for preparing N,N-diglycidylalkylamine represented by the formula(1) comprises the steps of: reacting alkylamine with epihalohydrin at atmospheric pressure and 10 to 100 deg. C in the absence of solvent and catalyst to prepare N,N-bis(3-halo-2-hydroxypropyl) alkylamine; and reacting the N,N-bis(3-halo-2-hydroxypropyl) alkylamine with an alkali metal compound, wherein R is saturated alkyl or unsaturated alkyl containing carbohydrate or carbon fluoride, or aromatic ring containing alkyl.

Description

The efficient synthetic method of N, N-diglycidylalkylamine

The present invention relates to a method for efficiently preparing an N, N-diglycidylalkylamine compound, and more particularly, by using an alkylamine and epihalohydrin as reactants without reacting a separate solvent and a catalyst. The intermediate, N, N-bis (3-halo-2-hydroxypropyl) alkylamine, is produced and then reacted with an alkali metal compound without separation or purification to yield high yield, high purity N, N-diglycidyl. A method for efficiently producing an alkylamine compound.

Generally, polyglycidyl compounds having a plurality of epoxy groups in one molecule are useful in various chemical materials industries such as raw materials for Gemini surfactants, intermediates for organic synthetic chemistry, monomers or crosslinking agents for polymer synthesis, and raw materials for crown ethers. The substance used.

Conventionally known methods for synthesizing glycidyl compounds are mainly prepared using alcohols and epichlorohydrin as reactants, and can be classified into three types as follows.

In the first known method, alcohols and epichlorohydrin are reacted under heating with a Lewis acid catalyst such as sulfuric acid, perchloric acid, and boron trifluoride while heating to about 60 ° C. to prepare chlorohydrin ether, and then an alkali is added to the chlorohydrin ether. A two-step method of cyclizing the molecule in addition is known [Japanese Patent Laid-Open No. 57-31921]. However, since the Lewis acid catalyst must be used in the conventional method, there is a problem such as corrosion of the apparatus, operational safety, and the like. After the first step of producing chlorohydrin ether in the production process, excess epichlorohydrin should be removed. In the second step, hydrophobic solvents such as xylene, toluene and benzene, and quaternary ammonium There is a disadvantage that the manufacturing process, such as the need to use a phase transfer catalyst and heated to 60 ~ 90 ℃ is very complicated.

The second known method, reported by M. Okahara, is a one-step method of simultaneously performing addition and cyclization reactions by reacting alcohols and epichlorohydrin in the presence of an aqueous alkali metal hydroxide solution and a phase transfer catalyst. It has been reported that cyl ether can be obtained in high yield of 54-89% [ Synthesis , 649 (1984)]. However, since alkali is mainly used in the form of an aqueous solution for ease of handling, the presence of this water causes side reactions in which the ring opening of the epoxy group or the alcohol is additionally added to the resulting glycidyl ether results in the formation of oligomers, polymers, and the like. There was a disadvantage in that the yield of the target diglycidyl ether is reduced, in particular, the shorter the distance between the two hydroxy groups had a disadvantage that the yield is significantly lowered.

The third known method is a method of reacting azeotropically removing water using an appropriate solvent to avoid side reactions caused by the presence of water in the reaction mixture (Japanese Patent Laid-Open No. 5-163260). However, the third method also has the disadvantage of using an azeotropic solvent, and additionally, a facility for separating and removing the generated water was required.

Therefore, in order to produce the desired glycidyl compound more economically and efficiently, it is necessary to technically solve the disadvantages of the known methods known to date.

Accordingly, the present inventors have made efforts to solve the problems of the conventional method for preparing glycidyl compounds, and as a result, when an alkylamine is selected instead of alcohol as a substance reacting with epihalohydrin, a separate solvent and Even in the absence of a catalyst, it reacts with epihalohydrin almost quantitatively to produce N, N-bis (3-halo-2-hydroxypropyl) alkylamine, which is a reaction intermediate. In the non-reactive state, it was found that various side reactions were prevented because the highly reactive epoxy group was not produced. In addition, the N, N-bis (3-halo-2-hydroxypropyl) alkylamine produced as the reaction intermediate was separated. Even if an alkali metal compound is added without separation or purification, halohydrin can be easily cyclized to prepare N, N-diglycidylalkylamine compound in high yield and high purity. The present invention has been completed by knowing that it can.

Accordingly, an object of the present invention is to provide a method for more efficiently preparing an N, N-diglycidylalkylamine compound.

In the present invention, N, N-bis (3-halo-2-hydroxypropyl) alkylamine is reacted by reacting an alkylamine with epihalohydrin at atmospheric pressure and at a reaction condition of 10 to 100 ° C. without using a solvent and a catalyst. It is characterized by a method for producing an N, N- diglycidylalkylamine compound represented by the following formula (1), characterized in that after the reaction to produce an alkali metal compound.

In Formula 1, R represents a saturated or unsaturated alkyl group containing a hydrocarbon or fluorocarbon, or an alkyl group including an aromatic ring.

Referring to the present invention in more detail as follows.

In the present invention, alkylamine and epihalohydrin are selected as reactants to react under solvent-free and catalyst-free conditions to produce N, N-bis (3-halo-2-hydroxypropyl) alkylamine as a reaction intermediate. It has the biggest feature in technology construction. Since the reaction intermediate produced according to the present invention does not include an epoxy group, unlike the conventional manufacturing method, it was possible to suppress side reactions caused by the reaction. In addition, since the reaction proceeds in a single phase, it has been used in the existing reaction using alcohols as a reactant. No phase transfer catalyst is needed. Therefore, the present invention maximizes the efficiency in the manufacturing process due to the reaction intermediate formed by the selective use of alkylamine as the reactant, and the catalyst-free and solvent-free reactions.

In addition, the present invention is to prepare the desired N, N- diglycidyl alkylamine compound by directly reacting the reaction intermediate prepared above with the alkali metal compound without a separate purification process, wherein the alkali metal in the solid phase or water It is possible to use both in liquid phase, which is another technical feature. Alkali metal is used as an aqueous solution in a conventional manufacturing method, but there was a problem of side reaction by water, but the present invention can use a solid alkali metal, thereby minimizing the reaction volume and solving the side reaction problem by water. The improvement of productivity can be expected.

Hereinafter, the method for preparing the N, N-diglycidylalkylamine compound according to the present invention will be described in more detail.

First, the alkylamine and epihalohydrin are reacted at room temperature or at a temperature slightly higher than the melting point of the alkylamine, which is the reactant, without the use of a separate solvent or a catalyst, and the reaction intermediate, N, N-bis (3-halo-2). -Hydroxypropyl) alkylamine. The reaction temperature varies depending on the type of amine, and in case of ethylamine and methylamine having low boiling points, an aqueous solution thereof is used as a reactant, and the reaction is performed at a temperature lower than 10 ° C. to prevent scattering of the reactants. . The alkylamine used in the present invention as the reactant preferably uses a primary alkylamine, but secondary alkylamine may also be used depending on the purpose. The epihalohydrin used for the reaction with the alkylamine is preferably used in a 2 to 4 molar ratio with respect to the alkylamine.

Next, the N, N-bis (3-halo-2-hydroxypropyl) alkylamine obtained as the reaction intermediate in the above, the alkali metal compound is directly added to the reactor without additional purification process N, N aimed at the present invention Prepare a diglycidylalkylamine compound. As the alkali metal compound, an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide, or the like is preferably used, and the alkali metal compound is preferably used in a 2 to 4 molar ratio with respect to the alkylamine. In the present invention, the alkali metal compound is used as a solid phase, but when using an amine having a low boiling point, water is included in the reaction mixture itself because the amine as a reactant is an aqueous solution.

In the following Reaction Scheme 1, N, N-bis (3-halo-2-hydroxypropyl) alkylamine is formed as a reaction intermediate by reaction of alkylamine and epihalohydrin, and an alkali metal compound Is an example of preparing an N, N-diglycidylalkylamine compound by reacting with sodium hydroxide.

In Scheme 1, R is a saturated or unsaturated alkyl group containing a hydrocarbon or fluorocarbon, or an alkyl group including an aromatic ring, and X represents a halogen element.

The reaction according to the invention is carried out in the range of 10 to 100 ° C. under atmospheric pressure. It is preferable that an object of the present invention does not use a separate solvent and a catalyst as a method for preparing a N, N-diglycidylalkylamine compound that does not use a solvent and a catalyst, that is, a separate solvent, water, and a phase transfer catalyst. However, in the case of methylamine and ethylamine used in the present invention, it is used in the form of an aqueous solution, and when the alkyl group is longer than the propyl group, it can be reacted without solvent.

In addition, upon completion of the preparation according to the process of the present invention described above, the reactants are dissolved in a suitable organic solvent such as hexane, cyclohexane, heptane, toluene, diethyl ether, dialkyl ether, and the like, followed by The sodium chloride, sodium hydroxide, etc. contained in the water can be removed by washing with water, and unreacted epichlorohydrin can be distilled off and reused. The desired diglycidylalkylamine product can be separated and purified through a simple distillation process.

Hereinafter, the present invention will be described in more detail with reference to the following examples, which are not intended to limit the present invention.

Example 1

37.39 g (0.4 mol) of epichlorohydrin (99%, Aldrich) was added to a 250 mL three-necked round bottom flask, and 4 g of naphthalene was added as an internal standard. A thermometer and a condenser are mounted in the reactor, and 7.77 g (0.1 mol) of methylamine aqueous solution (40%) is slowly added for 20 minutes while keeping the temperature inside the reactor below 10 ° C by using ice water and stirring with a magnetic bar. Added dropwise. Care must be taken that the internal temperature of the reactor during the dropping does not exceed 10 ° C. After the reaction was carried out for 5 hours while maintaining the reaction temperature 10 ℃, 32.98 g (0.4 mol) of NaOH aqueous solution (50%) was added and the reaction was terminated after 3 hours.

As a result of GC analysis using the internal standard, the analysis yield of diglycidylmethylamine was 91.5%.

Example 2

In the same manner as in Example 1, the purification method of the reaction mixture obtained by the reaction was carried out as follows.

Dissolve in 100 mL of water, transfer to a separatory funnel, wash the reaction vessel with 50 mL of n-hexane, place in a separatory funnel, shake vigorously, and stand still to separate the n-hexane layer. The layers were combined. 10 g of anhydrous sodium sulfate was added to this n-hexane solution to remove water, and the mixture was filtered to obtain a mixture. The mixture was distilled under reduced pressure to remove the solvent, and then distilled using Kugelrohr to obtain 13.16 g (yield: 91.9%) of diglycidylmethylamine. Distillation conditions at this time is 40 ℃, 53 mT (vacuum degree).

Example 3

In a 100 mL two-necked round bottom flask was placed 16.57 g (0.1783 mol) of epichlorohydrin (99%, Aldrich) and 2.90 g (0.045 mol) of ethylamine (70% by weight aqueous solution, Aldrich). 2 g of naphthalene (99%, Aldrich) was added as internal standard. After the condenser was installed in the reactor, the reaction temperature was maintained not to exceed room temperature using a water bath, and stirred for 6 hours using a magnetic straw. After confirming that the primary reaction was terminated by gas chromatography, 7.28 g (0.1783 mol) of sodium hydroxide was added thereto, followed by stirring for 1 hour to terminate the reaction. The analysis yield of diglycidylethylamine by gas chromatography analysis was 90.03%.

The reaction mixture obtained above was carried out in the same manner as in Example 3, and the results are shown in Table 1 below.

Example 4

In a 100 mL two necked round bottom flask was placed 16.57 g (0.1783 mol) of epichlorohydrin, 2 g of naphthalene and 4.60 g (0.045 mol) of hexylamine. The condenser was installed in the reactor and stirred at room temperature for 4 hours using magnetic milk. 7.28 g (0.1783 mol) of solid sodium hydroxide were added and stirred for 1 hour to terminate the reaction. Analytical yield of diglycidylhexylamine by gas chromatography analysis was 94.35%.

The reaction mixture obtained above was carried out in the same manner as in Example 3, and the results are shown in Table 1 below.

Example 5

In a 100 mL two-necked round bottom flask, 16.57 g (0.1783 mol) of epichlorohydrin, 2 g of naphthalene and 8.51 g (0.045 mol) of dodecylamine were added. The condenser was installed in the reactor, and after stirring for 4 hours using a magnetic milk at 40 ℃, 7.28 g (0.1783 mol) of sodium hydroxide was added and stirred for an additional 30 minutes, and then terminated. Analysis yield of diglycidyl dodecylamine by gas chromatography analysis was 92.42%.

The reaction mixture obtained above was carried out in the same manner as in Example 3, and the results are shown in Table 1 below.

Comparative example

In the same manner as in Example 1, a one-step reaction in which NaOH aqueous solution was added dropwise before adding an aqueous methylamine solution (40%) was performed. As a result of GC analysis using the internal standard, the analysis yield of diglycidylmethylamine was 36.2%.

division Example 1 Example 2 Example 3 Example 4 Example 5 Comparative example Yield (%) 91.5 91.9 90.03 94.35 92.42 36.2

As shown in Table 1, Examples 1, 3, 4 and 5 according to the present invention showed that the yield is significantly increased compared to the comparative example prepared by the conventional method. In addition, Example 2 measured the yield of the compound prepared in Example 1 through the purification process showed that the separation and purification according to the present invention is made very efficiently.

As described above, the present invention is excellent in the following effects and is useful for the application of industrial production.

First, since the reaction intermediate does not contain an epoxy ring by using an alkylamine instead of alcohols as a reactant, no side reaction occurs, thereby obtaining a product having high yield and high purity.

Second, even if the reaction temperature is maintained at room temperature or the melting point of the alkylamine (in the case of a solid at room temperature), the reaction proceeds well, thereby saving energy.

Third, since the reaction solution consists of a single phase, it is not necessary to add a separate phase transfer catalyst, so the manufacturing process is economical and easy to purify.

Fourth, solid alkali metals are added directly to the reactor, so there is no need for an apparatus for producing an aqueous alkali solution, and easy to separate and handle, and solidify by-products containing excess water generated in a process using an aqueous alkali metal solution. Or a device for neutralizing the aqueous base solution used in excess.

Fifth, since the reaction solvent is not used, the reactor volume can be minimized, so the productivity is high compared to the reactor size.

Claims (3)

The alkylamine was reacted with epihalohydrin at atmospheric pressure and at a reaction condition of 10 to 100 ° C. without using a solvent and a catalyst to produce N, N-bis (3-halo-2-hydroxypropyl) alkylamine as an intermediate. Thereafter, a method for producing an N, N-diglycidylalkylamine compound represented by the following Chemical Formula 1, which is prepared by reacting with an alkali metal compound: [Formula 1] In Formula 1, R represents a saturated or unsaturated alkyl group containing a hydrocarbon or fluorocarbon, or an alkyl group including an aromatic ring. The method for producing an N, N-diglycidylalkylamine compound according to claim 1, wherein the epihalohydrin is used in an amount of 2 to 4 molar ratio with respect to the alkylamine . The method for producing an N, N-diglycidylalkylamine compound according to claim 1, wherein the alkali metal is used at a molar ratio of 2 to 4 relative to the alkylamine .